Hydroxyacetylated and oxidized dimer of 9,11-linolo-diricinolein, and method of making same



in the two aforementioned patents.

Patented Aug. 26, 1947 HYDROXYACETYLATED AND OXIDIZED DIMER OF 9,11-LINOLO-DIRICINOLEIN, AND METHOD OF SAME Melvin De Groote, St. Louis, Mo., assignor to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware N Drawing. Original application July 13,1945,

Serial No. 604,992. Divided and this application May 17, 1946, Serial No. 670,534

Claims.

This invention relates to certain new chemical products or compounds.

The new chemical product herein described, particularly when-employed as a, demulsifier, consists of an hydroxyacetylated (including polyhydroxyacetylated) and oxidized dimer of 9,11- linolo-diricinolein. Oxidation and hydroxyacetylation have been applied to castor oilin order to produce a product having utility in demulsification of crude petroleum emulsions. U. S. Patent No. 2,340,305, dated February 1, 1944, to De Groote et a1., sis-concerned with a drasticallyoxidized hydroxyacetylated ricinoleic acid compound such as castor oil. Similarly, US. Patent No. 2,340,306, dated February 1, 1944, to De Groote et al., is concerned with a hydroxyacetylated, drastically-oxidized castor oil. Similarly, U. S. Patent No. 2,340,308, dated February 1, 1944, to

,De Groote et al., is concerned with a similar type of demulsifier in which a comparatively large proportion of hydroxyacetic acid is employed so as to produce a polyhydroxyacetic acid radical.

I have found that when castor oil is replaced by the dimer of9,11'-linolo-diricinolein,.one obtains new chemicalcompounds or products which are particularly valuable for numerous purposes and are particularly effective as demulsifying agents. Moreover, the two procedures involved, to wit, oxidation and hydroxyacetylation, can be conducted stepwise, one after the other in either direction, but may, in preparing derivatives of 9,11-linolo-diricinolein dimer be conducted simultaneously, and thus, afiord a distinct advantage, in comparison with the description of the products derived from castor oil, as disclosed For that matter, castor oil, diricinolein, diolein, and th'e like, may be subjected to hydroxyacetylation to yield a product of value in .demulsification of petroleum emulsions. See U. S. Patent No. 2,340,355, dated February 1, 1944, to Wirtel.

I my .co-pending application Serial No. 604,991, filed July 13, 19,45, it'has been pointed out that oxidationalone of 9,11-lino10+diricino1ein dimeryieldsa valuable product fordemulsification. Since the herein contemplated product, or productsmaybeprepared by first subjecting the specified .dimer to oxidation and then following by hydroxyacetylation, it may be most convenient to .repeat much of what is said in my co-pending application Serial No. 604,991, filed July 13, 1945, in regard to the preparation of an oxidized dimer of 9,1l linolo-diricinolein.

Oxidation is efiected by means of a gaseous oxygen-containing medium, particularly moist or dry air, andis conducted in the manner com- (9,11-linolcic acid) United States patents which illustrate this procedure. are the following: No. 2,140,271, dated December 13, 1938, to Schwarcman; No. 2,195,255, dated Mar. 26, 1940, to Priester; No. 2,209,065, dated July 23, 1940, to Pelikan; No, 2,212,385, dated Aug. 20, 1940, to Brod; No. 2,226,830, dated Dec. 31, 1940, to Priester; No. 2,226,831, dated Dec. 31, 1940,'to Priester; No. 2,246,768,-dated June 24, 1941, to Ubben; No. 2,261,663, dated Nov. 4, 1941, to Rheineck; No. 2,836,186, dated Dec. 7, 1943, to Nessler; and No. 2,351,444, dated June 13, 1944, to Miller.

The mixed isomers may be treated so as to convert the unconjugated isomer into the conjugated isomer, This isomerization reaction may be indicated thus:

HHHHH (9,12-linoleic acid) (9,11-linoleic acid) U. S. patents exemplifying isomerization procedure of the kind indicated, are the following: No. 2,185,414, dated Jan. 2, 1940, to McKinney; No. 2,242,230, dated May 20, 1941, to Burr; and No. 2,350,583, dated June 6, 1944, to Bradley.

9,11-lino1eic acid of approximately 80% to 85% purity is obtainable in the open market and also available intheform of the ethyl or methyl ester. Ignoring matters of cost, I prefer to prepare the monomeric mixed glyceride from this particular product. Methyl or ethyl ricinoleate, which can be prepared in the usual manner or purchased inthe open market, is reacted in the customary mannerwith glycerol monochlorohydrin, using two moles of the ester for two moles of the chlorohydrin. The reaction may be indicated thus:

V i --i H r/ aaOHCOiOCIh HE I uHaOHCOEOCEh HEOOH I i The 9,11-linoleic acid is converted into the anhydrous sodium salt and reacted mole for mole with the above intermediate in the presence of anhydrous alcohol or some other suitable solvent. This reaction may be indicated thus:

I "'I camioi Naio 0 0.017133,

CnHazOHCOO In regard to the above esterification procedure or alternate procedure, see the comprehensive article entitled Polyhydric alcohol esters of fatty acids, in Chemical Reviews, volume 3, No. 3, at page 257.

The polymerization of the diene acid is conducted in the ame identical manner employed for the polymerization of the methyl ester. The polymerization of'the methyl ester is described in various patents, as, for example: U. S. Patent No. 2,325,040, dated July 27, 1943, to Cook et al.; No. 2,347,562, dated April 25, 1944, to Johnston; and No. 2,357,839, dated Sept. 12, 1944, to Evans et al.

The .dimerization of the methyl ester. may be indicated in the following manner:

2 mole methyl ester 9,11-octadecadienic acid (originally present and/or formed by isomerization of 942 isomer) CHI (See U, S. Patent No. 2,347,562, dated April 25, 1944, to Johnson, above mentioned.)

In polymerization of polyene acid esters, it has been found that temperatures between about 250 C. and about 350 C. are suitable for polymerization. The time required for this polymerization varies not only with the temperature, but with the acid and the particular ester which is used. Generally, a period of from about onehalf an hour to about 50 hours is suitable, and in most instances, the polymerization may be efiected in not over 12 hours. If a conjugated unsaturated ester, such as the methyl ester of eleostearic acid be employed, a sufficient degree of polymerization may be obtained within onehalf to one hour at about 300 0., whereas, the methyl linolenates and linoleates generally require from about 5 to 12 hours or more. To speed up the polymerization process, suitable catalysts may be added, examples of which are: Fullers earth (preferably acid-treated), bentonite (preferably acid-treated), stannic chloride, etc. If catalysts be employed, it is sometimes possible to use lower temperatures and/or shorter periods of time than those indicated above. Substantially the same conditions may be used for dimerization, provided, however, that they must be below the point where dehydration of the ricinoleic acid radical takes place. In other words, in the present instance, the upper temperature limit is approximately 250 0., and, as a result of a somewhat lower temperature, it is sometimes desirable to use a longer time period for isomerization, for instance, a. time period as long as twenty-four to forty-eight hours.

Other means for inducing or hastening or catalyzing polymerization of the above described reactants are well known. See, for example, U. S. Patent No. 2,207,686, dated July 9, 1940, to

Schwarcman.

In any event, any suitable procedure is used to prepare the mixed glyceride, which has the following formula:

Suchv mixed. glyceride is then dimerized. in the manner previously described to produce the dimer of the following formula:

onomnonorromon=on cm 70o :011 0113(0mmnoncmozhomora)vooogn examination of thepreceding formula immediately suggestsadditional' procedures for producing the dimer of the mixed. glyceride. For instance, araw material whichcan be readily prepared. or purchased in the open market isdiricinolein. The formula for-suchproduct, ignoring isomeric forms; is, ofcourse:

Itbecomes, obvious that. if two moles .of diricinolein could be reacted with one. mole of the dimeric acid which has been previously depicted inthe form of a methyl ester, one would then obtain the d'imerized mixed. glyceride. previously described. The objection tosuch procedure;howevenis-that reaction. cannot be limited. tothe hydroxyl; attachedto-the glycerolresiduaand; in: fact, mayinvolve the ricinoleyl. hydroxylradical. Thus, such procedure. although. giving: fair-yields; also gives admixture withother products which". pref erab-ly are avoided. However, if. themethyl ester orethyl'esterofthe dimeric acidisused so esterification. involves. theelimination o-f'the methyl or ethyl alcohol, thensandin that event, the reaction appears to be limited; largely to involving the glycerol hydroxyl'.

Another procedure which immediately suggests. itself in. the formation. of the. monomeric. mixed glyceride is-the procedure commonly referred to as, re-esterification, cross-esterification, or trans-. esterification.v Such procedure is wellv known, andin. essence, would involve, for. example,.mixing two-moles of. triricinoleinwithone mole of; the total or. completev glyceride off 9,'11-lin.o'leic. acid.. Such migration of. the acylradicals. takes place at.a..temperature.belowthe pyrolytic point of ,triri'cinol'ein. and in the. presence ofan alkaline catalyst. The. suitable temperaturev is approximately 250. (1., orsli'ghtlyless,-.and'tlie, timerequired may. flue-comparatively long, for instance, 36 to 72 hours.

In ,any. event, one obtains. the. dimerized. mixed glyceride by any suitable procedure, and. theproduct employed should preferably contain at least 65% or-m'ore of the dimerized mixed glyceride, and some of theprocedures above enumeratedwill yielda product.markedly. inexcess of this. value. Such. mixed glyceride,.if; carefully prepared, has a viscosity approximately that of castor oilor slightly blown castor oil, a distinctly darker'color; and perhapsa-less pleasant odor. The chemical constants, such: as molecular weight; iodine: number; hydroxyl .number; and sat-- ponification: value, approximate: the) calculated i etc;

theoretical. value. It is, to be noted; that; this intermediateis not claimed herein perse.

It-iswell known.thatricinoleic,acidlcompounds,. particularly castor oil, can beoxidized in various ways; This is usually accomplished by subjecting a-ricinoleic compound to treatment such" as blowing with. a suitably gaseous: oxidizing me;- dium, e; g., air, oxygen; ozone, or ozonized air; Such oxidation is commonly carried out at ordinary or superat'mosphericpressure (up to' about 20-0" lbs. per'square inch) either moist orqdry;

and'iin thepresence or absence ofa catalyst, such:

as lead oleate, cobalt linoleate, or manganese oleate, or: suchas alpha-pinene or linseed oil,

Care should be taken, however,.not-to:permit temperature rise such; that. excessivepyro:-

lytic decompositionwould: take place. The oxidation: may be. vigorous, as by vigorousblowing, or; may be: more gradual, as byexposurein thinfilms toair, provided the oxidation is sufiiciently' prolonged to obtainthe desired drastic oxidation;

Generally, the time required is at least about -8' to l'0 hours, under conditions mostfavorable: to=

oxidation,.e. g;, blowing at a relatively high temperature, and for-certain fatty'compounds, much more. prolonged oxidation, e; g., several days, or

even weeks, is desirable, especially under condittions lessfavorable'torapid oxidation. Inany event, whether the'oxidationis produced by continued mild oxidation, or by more vigorous oxidation, a condition-of drastic oxidation is indicated by changes in chemical andphysical prop erties of the material. Thus changes are usually indicatedby a lowerediodine value, an increased: saponificationvalue, usually anincreased acetyl value, an increased'specific gravity, and an increased refractive index. Thus,.the iodine numher may become less than 70; and even as low as about 40.

creased and the drastically-oxidized product may become very heavy and stiff'at-ordinary'temperatures. The refractive index is also increased;

The color of the drastically oxidized material maybe a pale yellow or light amber, or may be a deep orange" color. on long enough, a product of liver-like consist-' ency: and dark:' color is obtained, but since such material ismore difficult to utilize. those" drastioally-oxidi'zed ricinoleic compounds which are pale'blownand havesome fluidity at normal tem peratures are preferred.

The same sort of procedure; which is used to oxidize castor oil or similar ricinoleic acid' de-- rivatives;.may be used to oxidize-dimerized 9,11- linolo-diricinolein. Generally speaking, however, the following modification should be kept in mind.

Such material may contain a small amount of 9.,l1'-linoleic acid or its ester resulting from incomplete polymerization. Such product is recognized as'a powerful catalyst for promoting, oxidation of castor oil or similar'materials. Thus; it is rarely necessary to add any catalyst to hasten. oxidation. Furthermore, it is: rarely. necessary to oxidize. under pressure, althoughsuch procedure may. be employed. It is rarely. necessary to use oxygen instead of air. Although any, suitable temperature, from C. or upwards, may be employed, it is my. preference to oxidize at a temperature of approximately C. to C. and-use a fairly long timeinterval, for

instance, two to eight: days;.notwithstandingathe:

The saponification value may be about 215 to 283,- and the acetyl' value maybe about to about 200. The viscosity is ine- If oxidation is carried fact that any of the usual procedures employed for oxidizing castor oil may be employed for oxidizing 9,11-1inolo-diricinolein, and generally speaking, considerably less drastic conditions are required. The time element can be decreased somewhat, and in some instances, can be decreased significantly, particularly if in the early stage there is present any appreciable amount of the catalyst above noted, either added or naturally present. The same sort of apparatus and the same sort of procedure is employed as in the case of conventional oxidation of castor oil. The product subjected to oxidation in the instant procedure has a viscosity somewhat greater than castor oil and seems to body somewhat more readily. One precautionary step is necessary, and that is, in the final stages of oxidation, the procedure must be conducted more cautiously than with castor oil. In any event, the material, prior to oxidation, should be analyzed and oxidation should be conducted until there is a sig- 7 is subjected to oxidation approximates that of castor oil, that is, around 90. If oxidation is drastic enough, the iodine number is reduced to approximately one-half its original value. One can readily produce three different grades, which, of course, show the efiect of increased or more drastic oxidation. One obtains a light blown and light-bodied material by reducing the original iondine value by approximately 25%. If oxidation is continued, or if more severe conditions of oxidation are employed, such as increased temperature, increased passage of air, or addition of catalyst, one can readily reduce the iodine number by a value equivalent to 26% to of the original value. Such material may be considered as a, medium-bodied, medium-oxidized material. Similarly, more extensive oxidation or more drastic oxidation will reduce the iodine value from 36% to in excess of 50% of its original value. Such product may be considered as heavy-bodied and heavily oxidized. Oxidation beyond this stage generally yields insoluble, or spongy, or rubbery masses.

In any event, the products herein contemplated are such that drastic oxidation by means of a gaseous oxygen-containing medium, results in a reduction in iodine number equivalent to at least 10% of its original value.

LIGHT-BODIED, LIGHT-BLOWN PRODUCT Dimerized 9,11-linolo-diricinolein is oxidized by dry air at a, temperature of 120 or somewhat in excess, for approximately four to five days, or slightly longer, so as to reduce the iodine value by 25% of its original value.

' MEDIUM-BODIED, MODERATELY-OXIDIZED PRODUCT The same procedure is followed as in Example 1, except the time of oxidation is extended by approximately two or three days, and the temperature raised slightly, if need be, so that at'the end of the period, the product shows a reduction in original iodine value equivalent to 33 /3% and an increased viscosity compared with the light blown product previously described.

HEAVY-BODIED, HEAVILY-BLOWN PRODUCT The same procedure is followed as in the preceding example, except that oxidation is extended a few days longer and a somewhat higher temperature employed, if need be, so as to reduce the iodine value by a percentage equivalent to almost one-half its original value.

The selection of suitable reactants in the manufacture of hydroxyacetylated or polyhydroxyacetylated, blown 9,11-linolo-diricinolein dimer is, of course, simple. The blown product may be analyzed so as to determine its hydroxyl or acetyl value. Such value may be interpreted on the basis of each fatty acid radical present, i. e., the total hydroxyl value, divided by four, represents the value equivalent to that of each aliphatic acyl radical. For convenience, the blown product may be considered as a tetrahydric alcohol having a molecular weight of 1828, and thus, one may obtain a monohydroxyactylated derivative, a dihydroxyacetylated derivative, a tri-hydroxyacetylated derivative, or even a tetra-hydroxyactylated derivative,

For purpose of convenience, reference will be made to mono-hydroxyacetylated blown 9,11- linolo-diricinolein, di-hydroxyacetylated blown 9,1l-linolo-diricinolein, tri hydroxyacetylated blown 9,1l-linolo-diricinolein, and tetra-hydroxyacetylated blown 9,1l-linolo-diricinolein.

Examination of the blown product, prior to hydroxyacetylation indicates values substantially as follows:

Acid number v v 10.5 to 36.3 Saponification number 200.0 to 300.0 Iodine number 40.5 to 65.0 Acetyl number 150.0 to 212.0 Hydroxyl number to 240 Percent unsaponifiable matter Not over 3% Percent ash Trace Examination of the reaction between hydroxyacetic acid and castor oil or hydroxyacetic acid and blown castor oil, or as in the present instance, hydroxyacetic acid and blown 9,11-1inolo-diricinolein, indicates that water is formed and removed. Actually, the wate formed may not necessarily be removed instantly, and thus, the Water present may enter into certain reactions. Likewise, for reasons of economy, it may be desirable to use a highly concentrated hydroxyacetic acid instead of the anhydrous material as the selected reactant. In such instances, the water would readily ente into hydrolytic reaction, and thus, the product or composition which is actually hydroxyacetylated, may include a variety of cogeneric materials. In addition to the other products formed by hydrolysis, glycerol may be included. Although it is believed, in view of what has been said, that no further description is necessary in regard to the manufacture of hydroxyacetylated compounds of the kind herein contemplated, the following examples are included by way of illustration:

HYDROXYACETYLATED BLOWN DIMER Example 1 One thousand pounds of the dimer described under the heading fLight-bodied, light-blown product, is treated with 84 pounds of concentrated hydroxyacetic acid containing 30% of water. The reaction is conducted at ZOO-250 C. for approximately 2 hours. Completenessin reaction is indicated by the fact that elimination of water practically ceases, decreas in acid value and hydroxyl value of mixtureandeliminationoi free hydroxyacetic acid. The procedure is conducted in the usual reaction vessel of the kind employed for esterification, and may be constructed of any material which is resistant to the reactants. The amount of hydroxyacetic acid selected in the present instance is calculated so as to give substantially a mono-hydroxyacetylated blown castor oil.

HYDROXYACETYLATED BLOWN 'DIMER Example 2 The same procedure is employed as iii-Example 1, preceding, except that twice the amount of hydroxyacetic acid'is used.

HYDROXYACETYLATED BLOWN DIMER Ea'amp le -3 The same procedure is followed as in Example 1, preceding, except that three 'timesthe amount of'hydroxyacetic acid is employed.

HYDROXYACETYLATED BLOWN DIMER Example 4 The same procedure is followed as in Example 1, preceding, except that four times the amount of hydroxyacetic acid is employed as a reactant.

The same procedure is followed as in'the five preceding examples, except'that'the reactant designated as Light-bodied, light-'blown-product, is replaced by the -blown dimer 'described'under the heading Heavy-bodied, heavily-blown product.

HYDROXYACETYLATED BLOWN DIMER Example 7 The same .procedureisfollowed as in Examples -1 to 6, preceding, except that anhydrous hydroxyacetic acid is employed and water is removed'immediately upon formation. The product so obtained represents hydroxyacetylated'blown 'castor oil, or more especially, 'hydroxyacetylatedblown triricinolein, in the presence of a minimum amount of hydroxyacetylated cogeners.

If the amount of hydroxyacetic acid employed is greater than that which can react with the available hydroxyl radical, then the hydroxyacetic acidpolymerizes in the same way that diricinolein, triricinolein, e'tc., is obtained "from monomeric r'icinoleic acid. Such acids are obvious'ly ester acids obtained by self-esterification.

The constitution of such polyhydroxyaceti'c acids and their relationship 'to hydroxyacetic acid, is readily shown'by the following formulae:

OI-ICHzCOOH OHCI-IzCOOCI-IzCOOH OHCI-IzCOOCHzCOCCHaCOOH OHCHzCOOCHzCQOCHzCOOCHzCOOH OHCI-IzCOOCHzCOOCHaCOOCHzCOOCI-Iz 'OHCHzCOOCHzCOOCI-IzCOOCHzCOOCHzCOOH OH(CH2COO) 11H 11 being at least 2 and not over 10.

In thepresent instance, however, the polyhydroxyacetic acids, in View of the previous limitation, based on amounts of reactants employed, are limited .to the dimeric specie or't'rimer specie of the structure It is obvious that such products are obtained by the same procedure indicated previously in .Hydroxyacetylated blown dimer, Examples 4, 5 and 6, and that part of Example 7 whichemploys the same stoichiometric ratio .of reactants. The only-difference in manufacturing procedure is employment of double, triple'or quadruple the amount of hydroxyaceti'c acid,

"In light :of what has been said earlier in this description, it is obvious that the oxidation reaction may be employed after hydroxyacetylation. This is comparable .to the process of manufacture employed in the aforementioned U. S. Patent No. 2,340,305. By way of illustration, the following examples are included:

HYDROXYACETYLATED DIMER Example 1 1,000 pounds of the dimer of thefollowing composition: 7

. CHKCHQ)5CH0HCH2CH=0H(CH2)7C.O 0%11 OHQ(GHZ)5CHOHCH2CH=CH(CHZMCOOCH I oH=cH having a hydroxyl value-of approximately 110, is treated with 200/220 pounds of concentrated hydroxyacetic acid containing 30% of water. The temperature employedis about 18'0205 C., for 6 to 16 hours, with elimination-of water, and in any event, until analytical testsshow an appropriate reduction in hydroxyl value. The reaction Ill-35S is stirred constantly during-reaction.

I-IYnaoxYAcErYLArEn DIMER Example 2 The sameprocedure is employed as in Example .1, preceding, except that twice the amount of hydroxyacetic acid is employed so as to obtain a di-rhydroxyacetylated dimer.

HYDROXYAGETYLATED DIM-ER Example 3 The same procedure is followed as in Example 1, preceding, except that three times the amount of hydroxyaceti acid isemployed so as toyield a substantially 'tri-hydroxyacetylated dimer.

I-IYDROXYACETYLA'IED DIMER Example 4 Theisa'me procedure islfollowed as in Example 1, preceding, except that four times the amount of hydroxyacetic acidis employed so as to obtain a tetra hydroxyacetylated-dimer.

I-IYnRoxYAcErYLA'rED; DIM R H I Example 5 V The same procedure is followed :as in'Example 1, precedi g, except that anhydrous hydroxyacetic acid is employed and Water is removed immediately upon formation. The product so ob-' tained represents hydroxyacetylated dimer, or more specifically, hydroxyacetylated 9,11-linolodiricinolein, in the presence of a minimum amount of hydroxyacetylated cogeners.

HYnRoxYAoErYLArEn DIMER Example 6 In light of what has been said previously, as to the utilization of polyhydroxyacetic acid and its derivatives, the same procedure is followed as in Example 4, preceding, and that part of Example which is an analogous composition, except that two times or three times as much hydroxyacetic acid is employed so as to introduce a di-hydroxyacetic acid radical or a trihydroxyacetie acid radical.

In the production of compounds of the kind herein described for various uses, and particularly for use as a demulsifier, it is to be noted that hydroxyacetylation and oxidation may take place simultaneously and need not take place in successive steps, as exemplified by similar procedures in connection with castor oil or its equivalent. Such procedures have been described in the aforementioned patents-U. S. Patents Nos. 2,340,305, 2,340,306 and 2,340,308.

As an example of such procedure, one need only mix the dimer with a predetermined amount of anhydrous hydroxyacetic acid or the 70% aqueous solution. The ratio of reactants employed correspond to those in the various prior examples. The mixture is agitated and heated to any convenient temperature, for instance, 165 to 205 C., with constant oxidation and stirring, so as to eliminate moisture and permit oxidation to take place more rapidly. Oxidation can usually be accomplished within ten to forty hours, and the resultant product, although perhaps different in degree, is not different in kind from the type of material obtained by either oxidation followed by hydroxyacetylation, or the reverse procedure.

Attention is directed to the fact that hydroxyacetic acid can undergo various pyrolytic or pyrogenic reactions forming a variety of materials other than the polyhydroxyacetic acids above noted. It has been my experience that when the temperature is held at 200 C., or slightly under, provided the reaction is not conducted to excessive lengths, as indicated by analytical determinations, there is comparatively little of such cogeneric compounds obtained, and the bulk of the compounds represent hydroxyacetylated derivatives or polyhydroxyacetylated derivatives. If a temperature perceptibly higher than this temperature is employed, for instance, 210. or higher, and particularly for any great length of time, and if the reaction is not stopped at completion, then and in that event, one may obtain a significant portion of other compounds, which, although not objectionable, may be equally suitable for the same purpose as herein contemplated.

OXIDIZED HYDROXYACETYLATED DIMER Example 1 A hydroxyacetylated dimer of the kind described under the heading Hydroxyacetylated dimer, Example 1, or Hydroxyacetylated dimer, Example 2, or Hydroxyacetylated dimer, Example 3 is oxidized by dry air at a temperature of 120 C. or somewhat in excess for approximatel2 ly four or five days, or slightly longer, so as to reduce the iodine value by 25% of its original value.

OXIDIZED HYDROXYACETYLATED DIMER Example 2 The same procedure is followed as in Example 1, except the time of oxidation is extended by approximately two or three days and th temperature raised slightly, if need be, so that at the end of the period, the product shows a reduction in original iodine value equivalent to 33 and an increased viscosity compared with the lightblown product previously described,

OXIDIZED HYDROXYACETYLATED DIMER Example 3 The same procedure is followed as in the preceding example, except that oxidation is extended for a few days longer and a somewhat higher temperature employed, if need be, so as to reduce the iodine value by a percentage to almost onehalf of its original value.

The new chemical products or compounds herein described are useful for other purposes, in addition to demulsification. They may be added, for example, to metal polishes to give a slight acidity. They may also be employed as a plasticizer in resin formation, where the acidity of the carboxyl is not objectionable. I have found that the chemical compounds herein described, which are particularly desirable for use as demulsifiers, may also be used as break inducers in doctor treatment of the kind intended to sweeten gasoline. (See U. S. Patent No. 2,157,223, dated May 9, 1939, to Sutton.) 7

Chemical compounds of the kind herein described are also of Value as surface tension depressants in the acidization of calcareous oilbearing strata by means of strong mineral acid, such as hydrochloric acid. Similarly, som members are effective as surface tension depressants or wetting agents in the flooding of exhausted oil-bearing strata.

As to using compounds of the kind herein described as flooding agents for recovering oil from subterranean strata, reference is made to the procedure described in detail in U. S. Patent No. 2,226,119, dated December 24, 1940, to De Groote and Keiser. As to using compounds of the kind herein described as demulsifiers, or in particular as surface tension depressants, in combination With mineral acid for acidization of oil-bearin strata,reference is made to U. S. Patent No. 2,233,383, dated February25, 1941, to De Groote and Keiser.

In the hereto appended claims, the product contemplated is described in terms of method of manufacture. The reason is obviously the same reason that makes it impossible to describe blown castor oil by structural formula or combination of structural formulae. In the first place, a variety of products are formed during oxidation, and in many instances, such products either have not been identified at all, or have partially been identified. To a marked degree, the chemistry of oxidation Of castor oil or my product, as herein described, is still'obscure. It is also to be noted that such mode of description has been used repeatedly in the patent literature.

Attention is directed to my co-pending application, Serial No. 604,991, filed July 13, 1945.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

13 1. In the process of manufacturing a hydroxyacetylated drastically oxidized dimer, the step of (A) oxidizing with an oxygen-containing gas at a temperature between 120 and 240 C. for a period of time sufiicient to produce a reduction in iodine value equivalent to at least per cent of the original value and not over 50 per cent of the original value, (B) hydroXy-acetylating said aforementioned drastically oxidized dimer.

2. The resultant product obtained in the process described in claim 1 wherein the oxygen containing gas is air.

3. The resultant product obtained in the process described in claim 1 wherein the oxygen containing gas is air, and the reduction in iodine value i the equivalent of at least 15 per cent and not over 25 per cent of the original value.

4. The resultant product obtained in the process described in claim 1 wherein the oxygen containing gas is air, and the reduction in iodine value is the equivalent of at least 26 per cent and not over per cent of the original value.

5. The resultant product obtained in the process described in claim 1 wherein the oxygen containing gas is air, and the reduction in iodine value is the equivalent of at least 36 per cent and not over per cent of the original value.

MELVIN DE GROO'IE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,347,562 Johnston Apr. 25, 1944 2,406,206 De Groote Aug. 20, 1946 

